TWI658920B - An additive manufacturing method of fabricating an object on a build stage and a metallic base material having a specific surface chemistry for use in additive manufacturing method - Google Patents

Abstract

The present invention relates to a method and apparatus suitable for performing an additive manufacturing process and products produced therefrom, and in particular, to an additive manufacturing process using an energy beam to selectively fuse a substrate to produce an object. More specifically, the present invention relates to methods and systems for using reactive fluids to actively manipulate the surface chemistry of a substrate before, during, and / or after an additive manufacturing process.

Description

Additive manufacturing method for manufacturing articles on established platform and metal substrate with specific surface chemistry for additive manufacturing method

This application claims priority from US Provisional Application No. 62 / 271,901, filed on December 28, 2015.

The present invention relates to a method and apparatus capable of performing additive manufacturing (AM) procedures and products produced by the same, and more particularly to an additive manufacturing procedure using an energy beam to selectively melt a material to produce an object. More particularly, the invention relates to methods and systems that use a reactive fluid to actively manipulate the surface of a material before and / or during the additive manufacturing process.

Additive manufacturing process (also known as multilayer manufacturing), also known as 3D printing, is a technology that has been established but is still mature. In its broad definition, the additive manufacturing process relates to the manufacture of a three-dimensional object, which is deposited into a net shape or near net shape (NNS) through the deposition of continuous layers of material. Additive manufacturing covers a variety of manufacturing and prototyping technologies known by many names, including freeform fabrication, 3D printing, rapid prototyping / tooling, and more. Additive manufacturing technology can manufacture complex components from a variety of materials.

While a large number of additive manufacturing processes are now available, a special additive manufacturing process uses an energy beam (such as an electron beam or electromagnetic radiation such as a laser beam) to sinter or melt a material (such as a powder , Cylinder, line, or fluid to create a solid three-dimensional Objects in which particles of powder material are linked together. The most commonly used methods for powder materials are electron-beam melting (EBM), selective laser melting (SLM) or direct metal laser sintering (DMLS), Selective laser sintering (SLS), fused deposition modeling (FDM), fused filament fabrication (FFF), or powder bed and inkjet head 3D printing 3DP), these powder layer procedures are referred to in this system as laser powder deposition or laser additive manufacturing (LAM). Selective laser sintering is a significant additive manufacturing process and enables rapid manufacturing of functional prototypes and molds by using a laser beam to sinter or melt a fine powder. More precisely, sintering requires melting (agglomerating) particles of the powder at a temperature below the melting point of the powder material, but melting requires completely melting the particles of the powder to form a solid homogeneous mass. The specific procedure for laser sintering or laser melting involves thermal transfer to a powder material and subsequent sintering or melting of the powder material. Although laser sintering and melting procedures can be applied to a wide range of powder materials, the scientific and technical aspects of production processes, such as the effects of sintering or melting rates and processing parameters on the progress of microstructures during the layer manufacturing process, have not been fully understood. This manufacturing method is accompanied by multiple modes of heat, mass, and momentum transfer, and chemical reactions that occur on the surface of the powder and complicate the process.

Although multiple laser additive manufacturing forms have high potential for manufacturing and repairing complex objects, they are limited by certain disadvantages that exist in the use of powder materials. One of the disadvantages is related to the reactivity of the surface of the powder material with elements in the air such as oxygen and nitrogen. When the powder material contains reactive metals such as iron, aluminum, and titanium, the surfaces of these metal particles can react with the gas to form microstructural defects (such as voids, impurities, or inclusions) in the final product. Such shortcomings can lead to catastrophic failure. These impurities include metal oxides and metal nitrides, and these disadvantages, whether they are impurities, voids or inclusions, their proportions will increase as the surface area of the powder material increases.

In the past, powder materials have been formed in low-oxygen environments to reduce unnecessary chemical reactions; however, the operation of low-oxygen powder materials in inert gas environments, from powder production to actual use in additive manufacturing processes, This increases the cost of powder production, powder size classification, delivery, and safety requirements. This is due to the high explosive properties of low oxygen metal powders. Of course. Unfortunately, the presence of oxides or other impurities on the surface of the powder material that is not so treated prevents the adhesion of the powder used to make the metal product, thereby reducing the mechanical properties of the finished product. The grain structure with more / larger pores and disordered grain arrangement caused by temperature gradient in the procedure also causes residual stress in the finished product.

Powder materials also easily absorb moisture, which in the case of metal powders leads to the formation of metal oxides, and also easily causes unwanted porosity in metal objects formed by laser powder deposition. For high-strength steel, moisture is also a source of hydrogen, which is formed on the surface of the powder and in the finished product, causing subsequent cracks or hydrogen embrittlement.

To further mitigate the harmful effects of air and moisture on powder materials, the melting pools created by laser powder deposition are often shielded by the use of a passivating gas such as argon and helium. However, such protection cannot remove existing oxides, which are easily formed outside the material powder during manufacturing, storage, and handling. As a result, these oxide-clad metal fillers must often be reduced during the melting process to avoid porosity and other disadvantages in forming metal deposits. Post-deposition processes such as hot isostatic pressing (HIP) are also often used to collapse pores (voids), inclusions and cracks to improve the properties of laser deposited metals. To avoid moisture absorption, metal powder fillers are often stored in pre-heated hoppers. Such protection and post-treatment methods are important for metal powders containing highly reactive metals (such as superalloys) and fine powders with high surface areas.

On the other hand, other techniques to mitigate the harmful effects of air have attempted to protect the melting pool generated by the deposition of laser powder to remove impurities by using a flux and powder materials. Please refer to US patent application US 2013/0136868. Fluxes avoid the reaction of the finished product with the gas in the air, such as shielding gases or the gas mixtures discussed above; however, the flux is a solid material and is sometimes added to the manufactured material.

Pre-treatment of virgin powder materials used in some additive manufacturing processes is often necessary. Pre-treatment may include coating, degassing, and heating the powder. Degassing can be used to remove moisture from powder particles. When exposed to the environment, the powder surface can be oxidized very quickly during the manufacturing process. Water vapor can be absorbed in the gaseous material, which can create voids in the material formed by the additive manufacturing process. The method of removing moisture from the manufactured material can cause the formation of hydrogen, which makes the final material more brittle. The previous methods for removing water vapor from the powder include a variety of degassing methods. For example In other words, Chinese patent CN105593185A describes a method for generating titanium oxide powder with low oxygen content by using hydrogen atmosphere and hydrogen embrittlement. However, avoiding the reaction system with oxygen leads to the complexity of safe transportation / operation because the low-oxygen metal powder system is highly explosive.

In addition, the conventional method uses hydrogen oxide to reduce a large amount of metal oxides at a high temperature sufficient to perform a reduction reaction after manufacturing using metal oxide pastes. Please refer to US patent application US 2013/0136868, which has also been found to be insufficient. Where the gas is difficult to invade and diffuse, it is difficult to reduce the oxide in the finished product. High temperature heat treatment of gases can cause sintering of unwanted powders.

In view of the above, it can be understood that there are some problems, disadvantages or disadvantages of laser additive manufacturing, and improved methods and equipment are needed to produce near-net-shape objects to end errors, and / or have high-quality surface processing, and / or Reduces or eliminates cracks, inclusions, and fine pores between deposited layers in a finished product. Accordingly, a laser additive manufacturing system is needed, which is an active operation that can reach the surface of a material by introducing at least one reactive fluid or fluid mixture before and / or during the additive manufacturing process. Or the fluid mixture reacts with the surface of the substrate, such as, but not limited to, a powder, plasma, cylinder, wire, or fluid, which is deposited such that different portions of the deposited substrate can be made to have different substrate properties. By controlling / improving / adjusting the surface of the substrate, the mechanical and / or chemical properties of the manufactured object can be enhanced by manipulation of the surface properties of the substrate.

The invention provides a method and a device, which are suitable for use in additive manufacturing technology, in which a reactive flow system contacts a substrate, such as, but not limited to, a powder, plasma, cylinder, wire, or fluid, where the reactive The flow system adjusts the surface of the substrate to achieve the desired chemical properties before, during, or after the application of an energy beam, which is used to selectively sinter (fuse) or melt the substrate To create a 3D object. The substrate includes a reactive substrate that can be adjusted to a desired chemical surface by a reactive fluid, and a non-reactive substrate having a surface that does not react with the reactive fluid. From the group consisting of solids and fluids.

According to a first aspect of the present invention, the chemical composition of the surface of the substrate is added. Before, during, and / or after the manufacturing process, it is controlled / improved / adjusted by introducing at least one reactive fluid or fluid mixture that can chemically react with the surface of the substrate. A fluid containing a gas mixture can be used instead of a purified gas (such as helium, argon, or nitrogen) or in the chamber itself outside the purified gas, as well as on a metal powder transfer line, in a metal powder transfer container, or used Metal powder receiver, and the gas mixture contains hydrogen, carbon monoxide or other chemically reducing surface oxides and / or gas components that clean or remove impurities on the surface of materials such as solid powders.

The present invention includes the treatment of materials by a gas or multiple gases, and the gas contains a gas mixture, which can be used to recycle, for example, used metal powder, so that the cost of the powder is reduced. At the same time, these gases (such as helium) with higher thermal conductivity can be used as a purge gas or an equilibrium gas, which effectively reduce the residual stress caused by temperature gradients.

The present invention may further use a gas containing a gas mixture to remove hydrogen from the substrate or manufactured product and / or intentionally oxidize the surface of the substrate. As mentioned earlier, hydrogen on the surface of the substrate and in the finished product is known to cause hydrogen embrittlement. According to the present invention, a gas system comprising a gas mixture with CO, CO ₂ and / or fluorocarbons is used to remove hydrogen to enhance the mechanical strength of the finished product.

The invention further considers the use of a gas containing a gas mixture to form nitrides, carbides, borides, phosphides, silicides or other chemical layers on the surface of the substrate, such as, but not limited to, metal powders to enhance the finished product Resistance to abrasion or corrosion.

Any combination of these gases can be used to form binary, ternary or higher order compounds simultaneously, such as nitrides and borides.

The present invention further contemplates that the gas / fluid containing its mixture can be used to change the alloy composition of the substrate before, during, and / or after additive manufacturing. Gases / fluids containing volatile organometallic components can be used to introduce or deposit metals onto the surface of the powder by chemical vapor deposition, atomic layer deposition, or other procedures, just as they are used in 3D printing procedures.

The present invention further contemplates that the use of a reactive fluid containing a mixture thereof is ideally suitable for use with an independent laser cutting process or in combination with a laser cutting process and an additive manufacturing process. In this example, the present invention contemplates that a manufactured object can be further shaped by the use of a laser, which is cut by melting, burning, or vaporizing a substrate. After and / or during the cutting, the surface of the finished article may be exposed to a reactive fluid and / or mixture thereof such that the entire surface of the finished article has the same required chemistry.

One of the technical effects of the present invention is the ability to improve mechanical properties. For example, metal products made by laser addition have higher wear resistance, higher corrosion resistance, higher mechanical strength, and lower Residual stress. Without wishing to be bound by any particular theory, it is believed that the mechanical and / or chemical properties of the finished product depend on the chemical composition and the granular structure of the matrix and surface of the manufactured product and the substrate used in the process. The presence of oxides or other impurities on the surface of the substrate prevents the adhesion of the substrate used to make the product, which reduces the mechanical properties of the finished product. The granular structure with more / larger pores and irregular grains caused by temperature gradient in the procedure also causes residual stress in the finished product.

Other embodiments and features are presented in the following description, and for those with ordinary knowledge in the art, after studying this specification, they can understand these embodiments and technical features to some extent, or they can be implemented by disclosing the embodiments And learned. The features and advantages of the disclosed embodiments can be understood and achieved through the tools, combinations, and methods described in the specification.

10, 210, 310‧‧‧ Additive manufacturing device

30, 230, 330‧‧‧ data files

40, 240, 340‧‧‧ Controller

42, 44‧‧‧ control signal

50, 250, 350‧‧‧‧ energy generation systems

60, 60 ’, 60”, 260, 260 ’, 260” ‧‧‧ reactive fluid

70, 270‧‧‧ substrate

80, 280, 380‧‧‧ inert gas

90, 290, 390‧‧‧ objects

100, 200, 300‧‧‧ Establish chambers

272‧‧‧Supply Line

370, 370 ’, 370” ‧‧‧ reactive fluid / substrate

The features and advantages of the present invention can be further understood by referring to the rest of the description and the drawings.

FIG. 1 is a schematic diagram of an additive manufacturing apparatus covering one aspect of the present invention, in which a reactive fluid and a substrate are in contact with each other in a building chamber.

FIG. 2 is a schematic diagram of an additive manufacturing apparatus covering one aspect of the present invention, wherein the reactive fluid and the substrate are in contact with each other before entering the establishment chamber.

FIG. 3 is a schematic diagram of an additive manufacturing apparatus covering one aspect of the present invention, in which a reactive fluid and a substrate are stored in the same container and are in contact with each other before entering the establishment chamber.

In the drawings, similar components and / or features may have the same reference numerals. In addition, multiple components with the same pattern can be distinguished by a bottom line or a second label. If only the first reference number is present in the description, the description is valid for similar elements having the same first reference number, regardless of the second reference number.

In the following, the use of a reactive fluid according to a preferred embodiment of the present invention in the additive manufacturing and the products made by it will be described with reference to related drawings. The same elements will be described with the same reference symbols.

The following definitions apply to the invention.

The use of additive manufacturing processes (AM processes) in the following is about any process that produces a useful, three-dimensional object and includes steps that sequentially form the shape of the object and one layer at a time. The additive manufacturing process includes electron-beam melting (EBM), selective laser melting (SLM) or direct metal laser sintering (DMLS), and direct metal laser melting (DMLS). direct metal laser melting (DMLM), selective laser sintering (SLS), fused deposition modeling (FDM), fused filament fabrication (FFF), powder layer nozzle 3D printing ( powder bed and inkjet head 3D printing (3DP), laser net shape manufacturing, direct metal laser sintering (DMLS), plasma transferred arc, freeform fabrication, etc. A specific type of additive manufacturing process uses an energy beam (such as an electron beam or electromagnetic radiation such as a laser beam) to sinter or melt a powder material. Additive manufacturing processes often use relatively expensive materials such as, but not limited to, powders, metal powder materials, cylinders, fluids, or wires as a raw material.

For the sake of clarity, the following description is for metal powders, but considers the use of any material, such as but not limited to powders, cylinders, fluids or wires, and should not be considered as a limitation. The present invention relates to an additive manufacturing process, which is a fast method for manufacturing an object (object, component, part, product, etc.), in which multiple thin unit layers are sequentially formed to produce the object. More specifically, multiple layers of a metal powder are laid and irradiated with an energy beam (such as a laser beam), so that the particles of the metal powder in each layer are sequentially sintered (fused) or melted to This layer or substrate is cured. According to one aspect of the present invention, at least one reactive fluid or fluid mixture that reacts with the surface of the metal powder or powders is brought into contact with the metal powder before, during and / or after the additive manufacturing process to actively operate the metal powder. Surface chemistry of powder materials, The chemical composition of the surface of such a powder material is controlled / improved / adjusted before, during, and / or after the additive manufacturing process. Gas components that contain hydrogen, carbon monoxide, or other chemically-reducible surface oxides and / or clean or remove impurities on the surface of solid powders without or with a purified gas (such as helium, argon, or nitrogen) The gas mixture is used to build the chamber itself, and on a metal powder transfer line, in a metal powder transfer container, or in a used metal powder receiver.

The present invention includes a bulk modification of a substrate, such as a polar film / layer (for example, less than 1 μm), by exposing it to a reactive fluid and using energy assistance (such as thermal diffusion in a semiconductor process). It is possible to adjust the nature of the whole.

The present invention includes the treatment of a substrate by a gas or multiple gases including a gas mixture, and can be used to recycle and reuse the used metal powder, which results in a reduction in the cost of the powder. At the same time, these gases (such as helium) with higher thermal conductivity can be used as a purge gas or an equilibrium gas, which effectively reduce the residual stress caused by temperature gradients.

The present invention may further use a gas containing a gas mixture to remove hydrogen from the powder or make a product and / or intentionally oxidize the surface of the powder. As mentioned earlier, hydrogen on the surface of the substrate and in the finished product is known to cause hydrogen embrittlement. According to the present invention, a gas system comprising a gas mixture with CO, CO ₂ and / or fluorocarbons is used to remove hydrogen to enhance the mechanical strength of the finished product. In addition to these gases, oxygen, ozone and / or hydrogen peroxide can also be used not only to remove hydrogen, but also to form metal oxide materials.

The invention further considers the use of a gas containing a gas mixture to form nitrides, carbides, borides, phosphides, silicides, or other chemical layers on the surface of the substrate to enhance the wear resistance or resistance of the finished product. Corrosive. Any combination of these gases can be used to form binary, ternary or higher order compounds simultaneously, such as nitrides and borides. The invention further contemplates that the gas / fluid containing its mixture can be used to change the alloy composition of the powder material before and / or during additive manufacturing. Gases / fluids containing volatile organometallic components can be used to introduce or deposit metals onto the surface of the powder by chemical vapor deposition, atomic layer deposition, or other procedures, just as they are used in 3D printing procedures.

For a detailed description of laser sintering / melting technology, please refer to US No. 4,863,538, Patents 5,017,753, 5,076,869 and 4,944,817. For this process, a laser beam is used to selectively fuse a powder material by scanning the cross-section of the material on a bed. These sections are scanned based on a three-dimensional description of one of the desired objects. The description can be obtained from a variety of sources, such as a computer aided design file, scanned data, or some other source.

In one embodiment, the additive process device includes a build chamber in which the article is manufactured, including a movable build platform located in the build chamber and the article is manufactured on the moveable build platform, including a substrate / fluid. A transmission system and an energy transmission system. The substrate / fluid transfer system transfers one of the chemically adjusted substrates to the build platform. In an alternative embodiment, a heating system may be used to heat the substrate and the platform with a heated gas. By conforming to the shape of the object, the substrate only needs to be given to some parts of the movable platform on which the procedure is performed.

According to some aspects of the present invention, the substrate may be a metal material, such as, but not limited to, aluminum and its alloys, iron and its alloys, titanium and its alloys, nickel and its alloys, stainless steel, cobalt chromium alloys, tantalum and niobium. The reactive flow system is selected based on the particular metallic material to be used and the desired surface chemistry. Reactive fluids include, but are not limited to, highly diffusive gases and / or gas mixtures such as reducing, oxidizing reagents, reactive gases, or reactive fluids. Gas components that contain hydrogen, carbon monoxide, or other chemically reduced surface oxides and / or clean or remove impurities on the surface of the substrate without or with a purified gas (such as helium, argon, or nitrogen) The gas mixture flow system is used to build the chamber itself, as well as on a substrate transfer line, in a substrate container, or in a used substrate receiver.

The method for producing a three-dimensional structure may include depositing a first layer of at least one of the aforementioned substrates on the platform to form a substrate. At least another layer of the substrate is deposited, and then laser scanning steps of successive layers are repeatedly performed to form a thicker substrate until a desired object is obtained. For manufacturing a three-dimensional structure, the substrate can be actively adjusted by changing the reactive gas during the layering process. The item is formed in layers until completion. In the present invention, the particle shape of the substrate used in one embodiment is not particularly limited. For powders, the average particle size is about 10-100 μm in one example. The properties of the metal powder or metal product are controlled during the manufacturing process by space-time (chamber / line / container, continuous / cycle / multi-step) during the additive manufacturing process The chemical reaction was improved.

In some embodiments, in addition to high dimensional accuracy and good microstructure characteristics, the present invention also provides a higher purity to the metal product, which has one of the substrate phase, crystal structure and metallurgical structure improvements, such as No microstructural disadvantages such as voids, impurities, inclusions, and special micro-cracks and porosity, and without the use of metal stamping, even if the product may be made of a pure metal and / or an alloy powder material Made, it is considered resistant to sintering. In addition, the present invention is to provide a methodology for adjusting the magnetic properties and residual stresses in a finished product.

The additive manufacturing process according to the present invention can be implemented in an inert gas environment, wherein the substrate has been stored in or reacted with a reactive fluid before entering the establishment chamber. In such an example, the inert gas environment includes a gas selected from the group consisting of helium, argon, hydrogen, oxygen, nitrogen, air, nitrogen oxides, ammonia, carbon dioxide, and combinations thereof. In one embodiment, the inert gas environment includes a gas selected from the group consisting of nitrogen (N ₂ ), argon (Ar), helium (He), and mixtures thereof. In one embodiment, the inert gas environment is substantially an argon gas environment. On the other hand, the additive manufacturing process according to the present invention is implemented under a gaseous environment of one of the required reactive fluids, wherein the substrate has been stored in or with the reactive fluid before entering the establishment chamber. Perform the reaction.

Please refer to FIG. 1, a schematic diagram of an additive manufacturing apparatus 10 is according to an embodiment of the present invention. As shown in FIG. 1, the additive manufacturing apparatus 10 includes a building chamber 100 having a movable building platform (not shown) on which an object 90 is manufactured. The additive manufacturing apparatus 10 further includes an energy generation system 50 and a controller 40. In an embodiment, when a reactive fluid 60 or a plurality of reactive fluids 60 ′, 60 ″ is introduced into the establishment chamber 100 of the additive manufacturing apparatus 10, it contacts the substrate 70 to generate a system by using The energy generated by 50 creates an object 90. When the substrate 70 contacts the reactive fluid 60, the surface of the substrate is adjusted as required to become the adjusted substrate 75 (not shown). The adjustment of the surface of the substrate 70 It can be the result of a chemical adjustment, a coating and / or the adsorption of reactive fluid 60. If necessary, the additive manufacturing device can introduce an inert gas 80. The object 90 can take many forms. The controller 40 is a transmission control Signal 42 goes to generation system 50 and sends control signal 44 to build chamber 100 to control the heating of the adjusted substrate 75 and in some embodiments the melting to form object 90. These control signals The numbers 42, 44 can be generated by using the design data 30.

The value set by the operator can be fed into the computer to set the amount and type of reactive gas to be contacted with the substrate 70, thereby allowing the operator to design the chemical pattern of the various layers within the object 90 during the manufacturing process. Different patterns and repeatability of the release of at least one reactive gas (60, 60 'and / or 60 ") depending on the method or process of the multilayer to be deposited may be defined and changed accordingly.

The description of the additive manufacturing apparatus 10 of FIG. 1 is not intended to suggest that physical and / or architectural constraints give different environments a method that can be implemented. For example, in other embodiments, as shown in FIGS. 2 and 3, the reactive gas system contacts the substrate at different times. For example, in one embodiment shown in FIG. 2, the reactive fluid 260 and the substrate 270 are in contact with each other on the supply line 272, thereby providing more time for chemical reactions to occur on the surface of the substrate 270. It is also helpful to expose the mixture of substrate and reactive gas 260 to a heating step, so the supply line 272 can deplete an external energy source (not shown) before being introduced into the setup chamber. Again, as previously described, the adjusted substrate (not shown) is then introduced into the creation chamber 200, in which the article 290 is manufactured. Another embodiment is shown in FIG. 3, which not only shows the benefits of adjusting the surface chemistry of the substrate, but also achieves enhanced safety, operability, and delivery of some substrates by storing and transferring the substrate with a reactive fluid 370 Sex. For example, fine particles or low-oxygen powders are explosive, and their handling and safety can be greatly increased by suspending them in the reactive fluid 370. Table 1 below provides various examples of reactive fluids and where reactions with metallic materials occur during the additive manufacturing process.

The additive manufacturing apparatus 10 shown in FIG. 1 can be established by adjusting an existing laser sintering or melting system. Different embodiments can be achieved by replacing the inert gas of these systems with a reactive gas.

One of the biggest difficulties in producing components using powder materials and the conventional laser additive manufacturing process is the high reactivity of the surface of the powder material with air and / or oxygen, which can cause residual stresses and defects during component manufacturing. As previously mentioned, by contacting a reactive fluid with a metal powder, it is believed that the amount of residual stress due to impurities, voids or inclusions can be reduced and thus a higher purity metal, component or product can be obtained. In addition, the operator of an additive manufacturing device can adjust the mechanical / chemical properties of each layer through the use of a reactive fluid, including the surface of the manufactured object, thereby providing some additional geometrical freedom and program robustness. In addition, it can also improve the effectiveness of material use, such as recycling, reducing waste, improving safety, operability and transportability of oxidizable powder.

In view of the above, the device 10 can handle a wide variety of materials, including but not limited to those described below.

Aluminum and its alloy: The substrate 70 may be pure aluminum or an aluminum alloy. The substrate 70 may also be a mixture of pure aluminum and particles of at least one aluminum alloy, or may be a mixture of multiple aluminum alloys. There is no limitation on the composition of an aluminum substrate 70, except that it contains enough aluminum in metal form for the powder material particles to form an enveloping film of aluminum on the body.

The substrate 70 may further include nickel and nickel alloys including nickel-based superalloys, copper and its alloys, Refractory metals, including precious metals and metalloids, and / or materials with high oxidation capabilities such as copper, iron, titanium, ruthenium, cadmium, zinc, rhodium, potassium, sodium, nickel, bismuth, tin, barium, germanium, lithium, strontium, Magnesium, beryllium, lead, calcium, molybdenum, tungsten, cobalt, indium, silicon, gallium, iron, zirconium, chromium, boron, manganese, aluminum, lanthanum, neodymium, niobium, vanadium, yttrium and / or scandium.

The substrate 70 may be a metallic glass or an amorphous metal compound, a ternary, quaternary or higher-order metal alloy having an amorphous structure, such as an aluminum-titanium-based alloy such as Ti-Al-Fe and Ti-Al-N, zirconium Base alloys such as Zr-Cu-Al-Ni, palladium-based alloys such as Pd-Ni-P, iron-based alloys containing iron, boron, silicon, carbon, phosphorus, nickel, cobalt, chromium, nitrogen, titanium, zirconium, vanadium and niobium Of combination. In manufacturing such metallic glasses, boron, phosphorus, silicon, carbon, and / or any element may be added to the device 10 by using a reactive fluid such as diborane, phosphine, and methane. The invention can be applied to form amorphous metal oxides, such as In-Ga-Zn-O and Zn-Rh-O. The oxide may be formed within the device 10 by using a reactive fluid such as oxygen or hydrogen peroxide.

The present invention can select a variety of reactive fluids, for example: (1) reducing agents: hydrogen, carbon monoxide, formic acid, ammonia, hydrazine, methylhydrazine, 1,2-dimethylhydrazine; (2) carbonizing agent / carbiding agent): saturated hydrocarbons such as methane, ethane, propane, butane, pentane, hexane, heptane and higher order hydrocarbons, unsaturated hydrocarbons, such as acetylene, propylene, butene Isomers, ethylene; (3) oxidants: carbon dioxide, oxygen, carbon tetrafluoride, trifluoromethane, difluoromethane, fluoromethane, hydrogen peroxide, ozone, nitrous oxide, nitric oxide, nitrogen dioxide, trioxide Nitrogen fluoride, fluorine; (4) Nitriding agents: methylamine, dimethylamine, trimethylamine, ammonia, hydrazine, methylhydrazine, 1,2-dimethylhydrazine; (5) boronizing agent: ethyl Borane, trimethylborane, tetramethyldiborane, trichloroborane, trifluoroborane; (6) curing agent: hydrogen sulfide, methyl mercaptan, ethyl mercaptan, propyl mercaptan, butane mercaptan , Pentyl mercaptan, dialkyl sulfide; (7) phosphating agent: phosphine, tert-butylphosphine, triethylphosphine, trimethylphosphine, phosphorus oxychloride, trifluorophosphine, phosphorus trichloride ; (8) Silane agents: silane, ethilanes, higher-order silanes, alkylsilanes, tetraethoxysilanes, fluorosilanes, chlorosilanes, aminosilanes; (9) selenizers: hydrogen selenide, alkylselenium Compounds; (10) plasma and supercritical fluids; (11) others: tungsten hexafluoride, trimethylaluminum, tetraethylaluminum, trimethylgallium, tetraethylgallium, titanium tetrachloride, transition metal compounds , Tungsten agent; and (12) combinations thereof

Unless defined otherwise, all technical and scientific terms used herein have the same meanings as those skilled in the art to which this invention belongs. Although many methods and materials similar or equivalent to those described in the present invention can be used in the practice of the present invention, the materials and methods according to some embodiments are described herein. Although the present invention has been described in detail with reference to some embodiments, those skilled in the art can perform many adjustments and changes therein. Without further elaboration, it is believed that those skilled in the art can use the present invention to the maximum extent by using the description of the present invention.

Where some embodiments have been disclosed, those skilled in the art will recognize that many adjustments, alternative constructions, and equivalents may be used without departing from the spirit of the embodiments of the invention. In addition, in order to avoid unnecessarily obscuring the present invention, many conventional procedures and elements are not described here. Accordingly, the above description should not be considered as limiting the scope of the invention.

When a range of multiple values is provided, it should be understood as each intermediate value between the upper and lower limits of the range (unless the context clearly indicates otherwise, or one tenth of the unit of the lower limit) is also disclosed, unless the context There are clear other instructions. Each smaller range between any mentioned value or intervening value in a stated range and any other referenced value or intervening value in that stated range are encompassed. The upper and lower limits of these smaller ranges can be independently included or excluded from the range, and each range is also covered by the present invention. One, two or zero limits are included in the smaller range. And subject to limits that are specifically excluded from the mentioned range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included.

According to the scope of the present invention and the patent application, "a" or "the" includes a plurality of indicating objects, unless the context clearly indicates otherwise. Thus, for example, "a procedure" includes a plurality of such procedures, and "dielectric material" includes one or more dielectric materials and equivalents thereof known to those skilled in the art.

In addition, "include" or "including" used in the present invention means the existence of the mentioned feature, whole, component, or step, but does not prohibit one or more other features, whole, component, step, action or group from being Join.

The above description is exemplary only, and not restrictive. Any equivalent modification or change made without departing from the spirit and scope of the present invention shall be included in the scope of the attached patent application.

Claims (30)

An additive manufacturing method for manufacturing an object on a building platform, comprising: depositing a first quantity of at least one reactive substrate to a building cavity by using at least one reactive fluid and at least one non-reactive substrate; A building platform in the chamber, the at least one reactive substrate has a surface that can be adjusted to a desired chemistry by the at least one reactive fluid, and the at least one non-reactive substrate has a surface that cannot be reacted by the at least one Fluid adjusting a surface; introducing the at least one reactive fluid into the establishing chamber to adjust the surface of the at least one reactive substrate, and applying energy to the surface of the at least one reactive substrate and the at least one A non-reactive substrate to melt the surface of the at least one reactive substrate and the at least one non-reactive substrate to form a first layer or a substrate; by depositing a second amount of the at least one reactive The substrate, the at least one non-reactive substrate or a combination thereof and applying energy to the second quantity of the at least one reactive substrate, the at least one non-reactive substrate or a combination thereof to the second quantity of the to A reactive substrate, the at least one non-reactive substrate, or a combination thereof is melted to the substrate to form at least another layer on the substrate; and each of the reactive substrate, the non-reactive substrate, or the substrate is continuously formed The combined layers are on the substrate until the manufacture of the object is completed. The additive manufacturing method according to item 1 of the scope of patent application, wherein the at least one non-reactive substrate is selected from the group consisting of a solid and a fluid. The additive manufacturing method according to item 1 of the scope of patent application, before applying energy to the at least one reactive substrate, the at least one non-reactive substrate, or a combination thereof, contacting the at least one reactive fluid with the at least one A reactive substrate, the at least one non-reactive substrate, or a combination thereof adjusts the surface of the at least one reactive substrate in the establishing chamber. The additive manufacturing method according to item 1 of the scope of patent application, wherein before depositing the second quantity of the at least one reactive substrate, the at least one non-reactive substrate, or a combination thereof on the substrate, A selected portion of the surface of the substrate is adjusted in the establishing chamber by the at least one reactive fluid contacting the substrate. The additive manufacturing method according to item 1 of the scope of patent application, wherein the adjusted substrate reduces at least one microstructure defect of the first layer and at least another layer, and the at least one microstructure defect is selected from the group consisting of impurities, A group of micro-cracks and porosity. The additive manufacturing method according to item 1 of the scope of patent application, wherein the adjusted surface of the at least one reactive substrate results in improvement of one of the substrate's phase, crystal structure, and metallurgical structure. The additive manufacturing method described in item 1 of the scope of the patent application, wherein the adjusted surface of the at least one reactive substrate results in an adjustment of the magnetic properties of the article being manufactured. The additive manufacturing method according to item 1 of the scope of the patent application, wherein the adjusted surface of the at least one reactive substrate results in adjustment of the residual stress properties of the manufactured object. The additive manufacturing method according to item 1 of the scope of patent application, wherein the at least one reactive substrate is selected from the group consisting of a powder material, a plasma, a cylinder, a wire, or a fluid. The additive manufacturing method as described in item 9 of the scope of patent application, wherein the powder material is a metal powder material. The additive manufacturing method according to item 10 of the scope of patent application, wherein the metal powder material is a metallic glass material or an amorphous metal compound material. The additive manufacturing method according to item 10 of the scope of patent application, wherein the metal powder material is a metal material that is easily oxidized, and the oxidation is caused by the reaction of air and / or oxygen with the surface. The additive manufacturing method according to item 10 of the scope of the patent application, wherein the metal powder material is a metal material that easily absorbs moisture. The additive manufacturing method according to item 12 of the application, wherein the at least one reactive substrate is selected from the group consisting of aluminum, nickel, iron, titanium, copper, refractory metals, and alloys thereof. The additive manufacturing method according to item 1 of the scope of the patent application, wherein the at least one reactive flow system is selected from the group consisting of a gas, a plasma, a supercritical fluid, and a combination thereof. The additive manufacturing method according to item 1 of the scope of the patent application, wherein the at least one reactive flow system is selected from the group consisting of a reducing agent, a carbonizing agent, an oxidizing agent, a nitriding agent, a boronizing agent, a sulfurizing agent, and a phosphating agent , Silanizing agent, selenizing agent, tungsten agent, carbiding agents and their combinations. The additive manufacturing method described in item 1 of the patent application scope further includes a step of cutting the manufactured object with a laser to form a new surface, and then exposing the new surface to the at least one reactive fluid. The additive manufacturing method described in item 1 of the scope of patent application, wherein the applied energy is an electron beam process. The additive manufacturing method as described in claim 17 of the scope of patent application, wherein part or all of the new surface can be adjusted to a desired chemical property by the reactive fluid. The additive manufacturing method according to item 1 of the scope of the patent application, wherein the surface that can be adjusted to a desired chemistry is coated with the reactive fluid. The additive manufacturing method as described in item 1 of the scope of the patent application, wherein the surface that can be adjusted to a desired chemistry is generated by absorbing the reactive fluid. An additive manufacturing method for manufacturing an object on a building platform includes: exposing a powder material to a reactive fluid to obtain a powder material being adjusted before being introduced into a building chamber; The adjusted powder material has a surface with a desired chemistry; the adjusted powder material is introduced into the build chamber having a build platform; a first amount of the adjusted powder material is applied to the build platform And applying energy to the first quantity of the adjusted powder material to fuse the plurality of particles of the adjusted powder material into a first layer or a substrate; by applying energy to at least one second deposited on the substrate An amount of the adjusted powder material and the second amount of the adjusted powder material particles are fused to the substrate to form at least another layer on the substrate; and each layer of the adjusted substrate is continuously formed on the substrate Up until the manufacture of the object is completed. The additive manufacturing method according to item 22 of the scope of patent application, wherein before being introduced into the establishing chamber, the surface of the powder material adjusted is adjusted to have a contact surface when exposed to at least one reactive fluid. A desired chemistry is adjusted on a surface of a substrate powder material. The additive manufacturing method according to item 22 of the scope of patent application, wherein the adjusted surface of the powder material reduces at least one microstructure defect of the first layer and at least another layer, and the at least one microstructure defect is selected A group of free impurities, micro-cracks, and porosity. The additive manufacturing method according to item 22 of the scope of the patent application, wherein the adjusted surface of the powder material results in improvement of one of the phase, crystal structure and metallurgical structure of the powder material. The additive manufacturing method according to item 22 of the scope of the patent application, wherein the adjusted surface of the powder material results in an adjustment of the magnetic properties of the manufactured object. The additive manufacturing method according to item 22 of the scope of the patent application, wherein the adjusted surface of the powder material results in adjustment of the residual stress properties of the manufactured object. An additive manufacturing method for manufacturing an object on a building platform. The object has enhanced mechanical strength. The method includes: storing at least one reactive substrate in a hydrogen-removing gas, and the hydrogen-removing gas system is selected from the group consisting of: In a group consisting of CO, CO ₂ , fluorocarbon or a mixture thereof, a hydrogen-free substrate is formed; the hydrogen-free substrate is introduced into a chamber having one of the establishment platforms; a first quantity of the A hydrogen-free substrate is applied to the building platform and energy is applied to the first amount of the hydrogen-free substrate to fuse the first amount of the hydrogen-free substrate into a first layer or a substrate. The additive manufacturing method according to item 28 of the scope of the patent application, wherein the applied energy is thermal diffusion. A metal substrate having a specific surface chemistry for use in one of the additive manufacturing methods described in any one of the claims 1 to 29, including: a container having at least one reactive fluid in contact with the Metal substrate.